One-pot fabrication of magnetic adsorbent based on polymeric ionic liquid/aminated carbon nanotubes composite for efficient capture of synthetic auxins in complex samples prior to chromatographic analysis.

Efficient enrichment is a challenging and indispensable step in the quantification of polar synthetic auxins in complex samples. In the current study, a new magnetic adsorbent based on polymeric ionic liquid/aminated carbon nanotube composite was fabricated with a one-pot precipitation copolymerization strategy and employed as the extraction phase of magnetic solid phase extraction of synthetic auxins. Various characterization techniques were utilized to inspect the morphology, structure, magnetic property, and functional groups of the prepared adsorbent. Under the optimal conditions, the obtained adsorbent displayed satisfactory capture performance towards studied auxins through multiple interactions. Adsorption studies evidenced that the adsorption procedure of the developed method towards analytes was fit for the Freundlich adsorption model and pseudo-second-order kinetics. Combining with high-performance liquid chromatography, sensitive and reliable method for the identification and quantification of trace synthetic auxins in environmental water and fruit juice samples was developed. The obtained limits of detection for water and fruit juice samples located in the ranges of 0.0059-0.013 and 0.018-0.031 µg/L, respectively. Recoveries in actual samples with different fortified contents varied from 82.2% to 117%, with satisfactory reproducibility. The results will evidence that the introduced extraction technique is a useful alternative for the entrapment of trace synthetic auxins from complex samples.

Preparation and application of a poly (ionic liquid)-based molecularly imprinted polymer for multiple monolithic fiber solid-phase microextraction of phenolic acids in fruit juice and beer samples.

In this work, a new molecularly imprinted polymer (MIP) using a poly (ionic liquid) (PIL) as a functional monomer was prepared and utilized as the extraction medium of multiple monolithic fiber solid-phase microextraction (MMF-SPME). A PIL, 1-ally-3-vinylimidazolium chloride, was used as a functional monomer, and 3,4-dihydroxybenzenepropanoic acid (DBA) and ethylene dimethacrylate were chosen as the template molecule and cross-linker, respectively, to synthesize the PIL/MIP. Under the optimized preparation conditions, the recognition coefficient of PIL-MIP for DBA was as high as 11.6. The combination of PIL/MIP-MMF-SPME and high-performance liquid chromatography with diode array detection (HPLC/DAD) was developed for the sensitive determination of phenolic acids (PAs) in fruit juice and beer samples. Under the optimal conditions which were investigated in detail, the limits of detection (LODs, S/N = 3) for PAs in fruit juice were 0.024-0.24 µg L-1, and the related values were 0.011-0.052 µg L-1 for the beer sample. The intra-day and inter-day precision (relative standard deviations, n = 4, %) at 1.0 and 100.0 µg L-1 spiking concentration were both less than 10%. In the analysis of PAs in fruit juice and beer samples, satisfactory recoveries and repeatability were achieved. In comparison with reported approaches, the proposed method exhibited some advantages including high selectivity, convenience, satisfactory sensitivity and environmental friendliness.

Determination of benzimidazole anthelmintics in milk and honey by monolithic fiber-based solid-phase microextraction combined with high-performance liquid chromatography-diode array detection.

A porous poly(methacrylic acid-co-ethylene dimethacrylate) monolithic fiber (MEMF) for solid-phase microextraction (SPME) of five benzimidazole anthelmintics was prepared by in-situ polymerization. The effect of polymerization conditions on SPME of the target analytes was studied thoroughly. The physicochemical properties of the monolith were characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy, and mercury intrusion porosimetry. Several conditions affecting the extraction efficiency were investigated and, under the optimized conditions, a simple and sensitive method for the determination of trace benzimidazoles residues in milk and honey was established by coupling MEMF-SPME with high-performance liquid chromatography-diode array detection (MEMF-SPME-HPLC-DAD). Under the optimum experimental conditions, the limits of detection (S/N = 3) of the method were 0.11-0.30 µg L(-1) for milk and 0.086-0.28 µg L(-1) for honey. Evaluation of intra-day and inter-day precision showed reproducibility was satisfactory-relative standard deviations (RSD) for both were <10 %. Finally, the method was successfully used for determination of benzimidazole residues in milk and honey. Recoveries obtained for determination of benzimidazole anthelmintics in spiked samples ranged from 72.3 to 121 %, with RSD always <11 %.

Fabrication and evaluation of a molecular-imprinted-polymer functionalized electrode for selective electric field-assisted solid-phase microextraction of phytohormones.

Specific extraction and separation plays a pivotal role in the accurate quantification of trace phytohormones (PHs). However, due to their high polarity, specific capture of PHs is challenging. In this study, under the assistance of electric field, a molecular-imprinted-polymer functionalized electrode (MIP@ED) was in-situ prepared using 3-indoleacetic acid (IAA) as template and employed as the adsorbent of electric field-assisted solid-phase microextraction (EA-SPME) for specific capture of PHs. Results showed that the implementation of electric field during the preparation of MIP@ED and EA-SPME procedures improved the extraction selectivity, the selective factors towards IAA and its structural analogues increased from 2.09 to 2.45 to 2.88-3.51. Under the optimum conditions, the proposed MIP@ED/EA-SPME was combined with HPLC technique to monitor trace PHs in water and agricultural products. The achieved limits of detection were in the ranges of 0.0053-0.011 µg/L and 0.048-0.12 µg/kg for water and agricultural product, respectively. The established approach was successfully applied to quantify trace PHs in real samples, and the spiked recoveries varied from 84.0 % to 118 % with good repeatability (RSDs blow 10 %). The obtained results provided clear evidence that the developed approach employing the MIP@ED/EA-SPME technique demonstrated high sensitivity, good selectivity, satisfactory reproducibility and environmental friendliness in the quantification of trace PHs in complex samples. In addition, the current study supplied a new strategy to enhance the specific recognition performance of MIP-based SPME.

New monolithic stir-cake-sorptive extraction for the determination of polar phenols by HPLC.

A novel porous monolith has been prepared and used as a sorbent in stir-cake-sorptive extraction (SCSE). The monolithic material was prepared by in-situ copolymerization of allyl thiourea (AT) and divinylbenzene (DB) in the presence of dimethylformamide as a porogen solvent. To optimize the polymerization conditions, different monoliths with different ratios of functional monomer to porogenic solvent were prepared, and their extraction efficiency was investigated in detail. The monolith was characterized by elemental analysis, scanning electron microscopy, mercury intrusion porosimetry, and infrared spectroscopy. Analysis of polar phenols in environmental water samples by a combination of ATDB-SCSE and HPLC with diode-array detection was selected as a model for the practical application of the new sorbent. Several extraction conditions, including extraction and desorption time, pH, and ionic strength of the sample matrix were optimized. The results showed that the new monolith had high affinity for polar phenols and could be used to extract them effectively. Under the optimum conditions, low detection (S/N = 3) and quantification (S/N = 10) limits were achieved for the phenols, within the ranges 0.18-0.90 and 0.59-2.97 µg L(-1), respectively. The linearity of the method was good, and the method enabled simple, practical, and low-cost extraction of these analytes. The distribution coefficients between ATDB and water (K(ATDB/W)) were calculated for the phenolic compounds and compared with K(O/W). Finally, the proposed method was successfully applied to the determination of the compounds in three environmental water samples, with acceptable recovery and satisfactory repeatability.

Preparation of magnetic poly(vinylimidazole-co-divinylbenzene) nanoparticles and their application in the trace analysis of fluoroquinolones in environmental water samples.

Nanosized spherical magnetic poly(vinylimidazole-co-divinylbenzene) particles were synthesized and used as a sorbent for the enrichment of trace fluoroquinolones (FQs) from environmental water samples. A suspension polymerization procedure was used to prepare the sorbent. The magnetic sorbent was characterized by SEM, transmission electron microscopy, elemental analysis, and FTIR spectroscopy. Analysis of enrofloxacin, marbofloxacin, fleroxacin, lomefloxacin, and sparfloxacin in environmental water samples by the combination of the magnetic sorbent and HPLC with diode array detection was selected as a paradigm for the practical application of the new adsorbent. Several extraction conditions, including desorption solvent, extraction and desorption time, pH value, and ionic strength in sample matrix, were optimized. Results showed that the new sorbent had high affinity for FQs and could be used to extract them effectively. Under the optimum conditions, low detection (S/N = 3) and quantification (S/N = 10) limits were achieved for the target analytes, within the ranges of 0.20-1.46 and 0.68-4.84 µg/L, respectively. Method repeatability was achieved in terms of intra- and interday precisions, indicated by the RSDs, which were both <10.0%. The method also showed good linearity, simplicity, practicality, and environmental friendliness for the extraction of FQs. Finally, the developed method was successfully applied to the determination of FQs in lake water, surface water, and reservoir water samples. Acceptable recoveries of spiked target compounds in these water samples were in the range of 52.1-104.5%.

Liposomes loaded with quercetin for resolution of lung inflammation in a lipopolysaccharide-induced mouse model of sepsis.

Quercetin (QU) has been widely used as a dietary supplement and proved useful to treat lung diseases. However, the therapeutic potential of QU may be restricted because of its low bioavailability and poor water solubility. In this study, we investigated the effects of developed QU-loaded liposomes on macrophage-mediated lung inflammation.In vivo, a mouse model of sepsis induced by lipopolysaccharide challenge was used to detect the anti-inflammatory effects of liposomal QU. Hematoxylin/eosin staining and immunostaining were utilized to reveal pathological damage and leukocyte infiltration into the lung tissues. Quantitative reverse transcription-polymerase chain reaction and immunoblotting were used to determine cytokine production in the mouse lungs.In vitro, mouse RAW 264.7 macrophages were treated with free QU and liposomal QU. Cell viability assay and immunostaining were utilized to detect cytotoxicity and distribution of QU in the cells. Thein vivoresults showed that liposomal encapsulation promoted the inhibitory effects of QU on lung inflammation. Liposomal QU decreased mortality in septic mice with no obvious toxicity on vital organs. Mechanistically, the anti-inflammatory effects of liposomal QU were associated with inhibition of nuclear factor-kappa B-dependent cytokine production and inflammasome activation in macrophages. Collectively, the results showed that QU liposomes mitigated lung inflammation in septic mice through inhibition of macrophage inflammatory signaling.

Speciation of organotin compounds in water and seafood samples by online hyphenation of porous polymer-based magnetism-enhanced in-tube solid phase microextraction and HPLC.

A new strategy based on online hyphenation of magnetism-enhanced in-tube solid phase microextraction (ME-SPME) and HPLC was developed for speciation of organotin compounds (OTCs) in water and seafood samples. Task specific porous polymer embedded magnetic nanoparticles (TPM) was fabricated in capillary and utilized as the microextraction column (MEC) of ME-SPME. The implement of magnetic field during extraction duration obviously improved extraction efficiencies of prepared TPM/MEC towards studied TOCs from 48.0-77.0% to 84.2-99.7%. Under the optimized extraction parameters, sensitive and automatic approach for the quantification of TOCs was developed by online hyphenation of ME-SPME and HPLC with fluorescence detection. The limits of detection for water and seafood samples were in the ranges of 0.0030-1.5 µg/L and 0.71-14 µg/kg, respectively. The established method was employed to measure low contents of studied OTCs in actual samples, and the recoveries at different fortified contents varied from 80.2% to 116% with satisfactory reproducibility (RSDs below 10%). In addition, confirmation experiments were adopted to inspect the accuracy of introduced method.

Robust genome editing in adult vascular endothelium by nanoparticle delivery of CRISPR-Cas9 plasmid DNA.

Vascular endothelium plays a crucial role in vascular homeostasis and tissue fluid balance. To target endothelium for robust genome editing, we developed poly(ethylene glycol) methyl ether-block-poly(lactide-co-glycolide) (PEG-b-PLGA) copolymer-based nanoparticle formulated with polyethyleneimine. A single i.v. administration of mixture of nanoparticles and plasmid DNA expressing Cas9 controlled by CDH5 promoter and guide RNA (U6 promoter) induced highly efficient genome editing in endothelial cells (ECs) of the vasculatures, including lung, heart, aorta, and peripheral vessels in adult mice. Western blotting and immunofluorescent staining demonstrated an ∼80% decrease of protein expression selectively in ECs, resulting in a phenotype similar to that of genetic knockout mice. Nanoparticle delivery of plasmid DNA could induce genome editing of two genes or genome editing and transgene expression in ECs simultaneously. Thus, nanoparticle delivery of plasmid DNA is a powerful tool to rapidly and efficiently alter expression of gene(s) in ECs for cardiovascular research and potential gene therapy.

Preparation, characterization and application of a new stir bar sorptive extraction based on poly(vinylphthalimide-co-N,N'-methylenebisacrylamide) monolith.

In this study, a new stir bar sorptive extraction (SBSE) coating based on poly(vinylphthalimide-co-N,N'-methylenebisacrylamide) monolith (SBSE-VPMB) was prepared. The influences of the contents of monomer in polymerization mixture and the percentage of porogen solvent on the extraction performance were investigated thoroughly. Several characteristic techniques, such as elemental analysis, scanning electron microscopy, mercury intrusion porosimetry and infrared spectroscopy, were used to characterize the monolithic material. The analysis of oxfendazole (OFZ) and mebendazole (MBZ) in milk and honey samples by the combination of SBSE with HPLC with diode array detection was selected as paradigms for the practical evaluation of the new coating. Under the optimized extraction conditions, the limits of detection (S/N=3) for OFZ and MBZ were 0.23-0.60 µg/L in milk and 0.24-1.08 µg/L in honey, respectively. The method also showed good linearity, repeatability, high feasibility and acceptable recoveries for real samples. At the same time, the extraction performance and the distribution coefficients (K(VPMB/W)) of OFZ and MBZ on SBSE-VPMB were compared with other SBSEs based on porous monoliths and commercial SBSE.

Porous monolith-based magnetism-reinforced in-tube solid phase microextraction of sulfonylurea herbicides in water and soil samples.

In the present study, porous monolith-based magnetism-reinforced in-tube solid phase microextraction (MB-MR/IT-SPME) was first introduced to concentrate sulfonylurea herbicides (SUHs). To realize the effective capture of SUHs, a monolithic capillary microextraction column (MCMC) based on poly (vinylimidazole-co-ethylene dimethacrylate) polymer doped with Fe3O4 magnetic nanoparticles was in-situ synthesized in the first step. After that, the MCMC was twined with a magnetic coil which was employed to carry out variable magnetic field during adsorption and desorption procedure. Various important parameters that affecting the extraction performance were inspected in detailed. Results well indicated that exertion of magnetic field in the whole extraction procedure was in favor of the capture and release of the studied SUHs, with the extraction efficiencies increased from 36.8-58.1% to 82.6-94.5%. At the same time, the proposed MB-MR/IT-SPME was online combined to HPLC with diode array detection (HPLC/DAD) to quantify trace levels of SUHs in water and soil samples. The limits of detection (S/N = 3) for water and soil samples were in the ranges of 0.030-0.15 µg/L and 0.30-1.5 µg/kg, respectively. The relative standard deviations (RSDs) for intra- and inter-day variability were both less than 10%. Finally, the introduced approach was successfully applied to monitor the low contents of studied SUHs in environmental water and soil samples. Satisfying fortified recovery and precision were achieved.

Development of solid-phase microextraction with multiple interactions-based monolithic fibers for the sensitive determination of perfluoroalkyl phosphonic acids in water and vegetable samples.

Due to highly fluorinated and di-anionic characters, it is great challenging to enrich perfluoroalkyl phosphonic acids (PFPAs). According to the unique chemical properties and molecular structure of PFPAs, a monolithic adsorbent using dodecafluoroheptyl acrylate and 4-vinylbenzyltrimethylammonium chloride as mixed functional monomers was synthesized and utilized as the extraction medium of multiple monolithic fibers solid-phase microextraction (MMF-SPME). Results well evidenced that the obtained adsorbent could enrich PFPAs effectively by means of multiple interactions including fluorophilic and anion-exchange interactions. Under the optimized synthesized and extraction conditions, a sensitive approach for the monitoring of trace levels of PFPAs in water and vegetable samples was developed by the combination of MMF-SPME and high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS). Limits of detection (LODs, S/N = 3) for water and vegetable samples were in the ranges of 0.00011-0.00086 µg/L and 0.0022-0.055 µg/kg, respectively. The introduced method was successfully applied to monitor target PFPAs in lake water, wastewater, pumpkin and cucumber samples. Recoveries at different spiking levels and the relative standard deviations for precision were in the ranges of 80.6-120% and 0.9-12%, respectively. Compared to previously reported approaches, the current method displays some merits such as simple operation, satisfactory sensitivity, low cost and eco-friendliness.

Dual functional monomers modified magnetic adsorbent for the enrichment of non-steroidal anti-inflammatory drugs in water and urine samples.

According to the molecular properties of non-steroidal anti-inflammatory drugs (NSADs), a new adsorbent for magnetic solid phase extraction (MSPE) was designed and synthesized. Triethyl-(4-vinylbenzyl)aminium chloride and 4-vinylbenzeneboronic acid were utilized as dual functional monomers to copolymerize with divinylbenzene on the surface of pre-modified Fe3O4 nanoparticles. The prepared magnetic adsorbent (Fe3O4@TCVA) was characterized by elemental analysis, Fourier transform infrared, scanning electron microscopy, transmission electron microscopy and vibrating sample magnetometer. Due to the abundant boronic acid, quaternary amine and phenyl groups, the Fe3O4@TCVA displayed satisfactory extraction performance for target NSADs (diclofenac acid, ibuprofen and mefenamic acid) by means of B-N coordination, anion-exchange, π-π and hydrophobic interactions. Under the optimized conditions, the Fe3O4@TCVA/MSPE was combined with high-performance liquid chromatography with diode array detection (HPLC-DAD) to sensitively analyze NSADs in water and human urine samples. Results indicated that the limits of detection for water and urine samples were in the ranges of 0.014-0.031 µg/L and 0.029-0.11 µg/L, respectively. The relative standard deviations for the intra-day and inter-day assay variability were below 10%. The applicability of the proposed Fe3O4@TCVA/MSPE-HPLC-DAD method was demonstrated by the successful extraction and quantification of trace levels of NSADs in real water and human urine samples. Satisfactory spiked recovery and reproducibility were achieved.

Direct enrichment of phenols in lake and sea water by stir bar sorptive extraction based on poly (vinylpyridine-ethylene dimethacrylate) monolithic material and liquid chromatographic analysis.

A poly (vinylpyridine-ethylene dimethacrylate) monolithic material was synthesized and selected as stir bar sorptive extraction (SBSE) medium. The influences of polymerization conditions on the extraction efficiency were investigated using phenol and p-nitrophenol as target analytes. Based on this, six strongly polar phenols in water were directly concentrated by the new SBSE and determined with high performance liquid chromatography equipped with diode array detector. To achieve the optimum extraction performance, several main parameters, including extraction and desorption time, pH value and contents of inorganic salt in the sample matrix were investigated. The method showed good linearity and acceptable recoveries, as well as advantages such as sensitivity, simplicity, low cost and high feasibility. The proposed method was successfully applied to the determination of phenolic compounds in lake and sea waters.

Polymeric ionic liquid-based portable tip microextraction device for on-site sample preparation of water samples.

On-site sample preparation is highly desired because it avoids the transportation of large-volume samples and ensures the accuracy of the analytical results. In this work, a portable prototype of tip microextraction device (TMD) was designed and developed for on-site sample pretreatment. The assembly procedure of TMD is quite simple. Firstly, polymeric ionic liquid (PIL)-based adsorbent was in-situ prepared in a pipette tip. After that, the tip was connected with a syringe which was driven by a bidirectional motor. The flow rates in adsorption and desorption steps were controlled accurately by the motor. To evaluate the practicability of the developed device, the TMD was used to on-site sample preparation of waters and combined with high-performance liquid chromatography with diode array detection to measure trace estrogens in water samples. Under the most favorable conditions, the limits of detection (LODs, S/N = 3) for the target analytes were in the range of 4.9-22 ng/L, with good coefficients of determination. Confirmatory study well evidences that the extraction performance of TMD is comparable to that of the traditional laboratory solid-phase extraction process, but the proposed TMD is more simple and convenient. At the same time, the TMD avoids complicated sampling and transferring steps of large-volume water samples.

Fabrication of polymeric ionic liquid-modified magnetic adsorbent for extraction of apolar and polar pollutants in complicated samples.

A new polymeric ionic liquid-modified magnetic adsorbent (PIL-MA) was successfully fabricated and used to extract apolar and polar pollutants with magnetic solid-phase extraction (MSPE). The PIL-MA was prepared by simple free radical copolymerization of 1-vinylbenzyl-3-methylimidazolium hexafluorophosphate, divinylbenzene and silica-coated magnetite. Several characterized techniques including infrared spectroscopy, elemental analysis, scanning electron microscopy, transmission electron microscopy and magnetic measurement were used to characterize the PIL-MA. Parabens and aromatic amines were selected as test analytes to investigate the extraction performance of PIL-MA for apolar and strongly polar analytes, respectively. The extraction parameters including the amount of PIL-MA, adsorption time, desorption solvent and time, pH value and ionic strength were optimized thoroughly. At the same time, convenient and sensitive analytical methods for parabens and aromatic amines in real samples were developed by the combination of PIL-MA-MSPE and HPLC-DAD. Results well demonstrate that there are abundant active groups in the PIL-MA and multiply interactions including π-π, hydrophobic, hydrogen-bonding and dipole-dipole are involved in the extraction.

Extraction of triazole fungicides in environmental waters utilizing poly (ionic liquid)-functionalized magnetic adsorbent.

This work prepared a new poly (ionic liquid)-functionalized magnetic adsorbent (PFMA) for the extraction of triazole fungicides (TFs) in environmental waters prior to determination by high performance liquid chromatography/diode array detection (HPLC-DAD). A polymerizable ionic liquid, 1-methyl-3-allylimidazolium bis(trifluoromethylsulfonyl)imide was employed to copolymerize with divinylbenzene on the surface of modified magnetite to fabricate the PFMA. The morphology, spectroscopic and magnetic properties of the new adsorbent were investigated by different techniques. A series of key parameters that influence the extraction performance including the amount of PFMA, desorption solvent, adsorption and desorption time, sample pH value and ionic strength were optimized in detail. Under the optimum conditions, the prepared PFMA could extract targeted TFs effectively and quickly under the format of magnetic solid-phase extraction (MSPE). Satisfactory linearities were achieved in the range of 0.1-200.0µg/L for triadimenol and 0.05-200.0µg/L for other TFs with good coefficients of determination above 0.99 for all analytes. The limits of detection (S/N=3) and limits of quantification (S/N=10) for TFs were in the range of 0.0050-0.0078µg/L and 0.017-0.026µg/L, respectively. Environmental waters including lake, river and well waters were used to demonstrate the applicability of developed MSPE-HPLC-DAD method, and satisfactory recoveries and repeatability were obtained.

Preparation of a polymeric ionic liquid-based adsorbent for stir cake sorptive extraction of preservatives in orange juices and tea drinks.

In this study, a new polymeric ionic liquid-based adsorbent was prepared and used as the extraction medium of stir cake sorptive extraction (SCSE) of three organic acid preservatives, namely, p-hydroxybenzoic acid, sorbic acid and cinnamic acid. The adsorbent was synthesized by the copolymerization of 1-ally-3-vinylimidazolium chloride (AV) and divinylbenzene (DVB) in the presence of a porogen solvent containing 1-propanol and 1,4-butanediol. The effect of the content of monomer and the porogen solvent in the polymerization mixture on the extraction performance was investigated thoroughly. The adsorbent was characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry. To obtain the optimal extraction conditions of SCSE/AVDVB for target analytes, key parameters including desorption solvent, adsorption and desorption time, ionic strength and pH value in sample matrix were studied in detail. The results showed that under the optimized conditions, the SCSE/AVDVB could extract the preservatives effectively through multiply interactions. At the same time, a simple and sensitive method by combining SCSE/AVDVB and high-performance liquid chromatography with diode array detection was developed for the simultaneous analysis of the target preservatives in orange juices and tea drinks. Low limits of detection (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target analytes were achieved within the range of 0.012-0.23 µg/L and 0.039-0.42 µg/L, respectively. The precision of the proposed method was evaluated in terms of intra- and inter-assay variability calculated as relative standard deviation (RSD), and it was found that the values were all below 10%. Finally, the proposed method was used to detect preservatives in different orange juice and tea drink samples successfully. The recoveries were in the range of 71.9-116%, and the RSDs were below 10% in the all cases.

Preparation of an adsorbent based on polymeric ionic liquid for the simultaneous extraction of acidic, basic and neutral pollutants.

In this study, coextraction of acidic, basic and neutral pollutants was realized with a new adsorbent based on polymeric ionic liquid (PIL). In the presence of a porogen solvent containing 1-propanol and 1,4-butanediol, an ionic liquid, 1-vinyl-3-octylimidazolium tetrafluoraborate was used as monomer to copolymerize with dual cross-linkers (divinylbenzene and N,N-methylene-bisacrylamide) to form the adsorbent for stir cake sorptive extraction (SCSE). Phenols, aromatic amines and parabens were selected as acidic, basic and neutral model analytes, respectively. The effects of preparation conditions and extraction parameters on the extraction performance of SCSE/PIL were investigated thoroughly. Under the optimized conditions, the prepared adsorbent showed satisfactory coextraction performance to the selected analytes with multiply interactions. At the same time, simple and sensitive analytical method for simultaneous determination of phenols, aromatic amines and parabens in environmental water samples was developed by the combination of SCSE/PIL with high-performance liquid chromatography with diode array detection. Low limits of detection (S/N=3) and quantification limits (S/N=10) of the proposed method for the targeted analytes were achieved within the range of 0.064-0.30µg/L and 0.21-0.99µg/L, respectively. The precision of the proposed method was evaluated in terms of intra- and inter-assay variability calculated as relative standard deviation (RSD), and it was found that the RSD values were all below 10%. Ultimately, the applicability of developed method was successfully confirmed by analyzing lake, reservoir and river water samples. Recoveries obtained for the determination of targeted analytes in spiking samples ranged from 70.0% to 112%, with RSDs within the range of 1.6-9.8%.

Sensitive determination of estrogens in environmental waters treated with polymeric ionic liquid-based stir cake sorptive extraction and liquid chromatographic analysis.

A simple, sensitive and environmentally friendly method using polymeric ionic liquid-based stir cake sorptive extraction followed by high performance liquid chromatography with diode array detection (HPLC/DAD) has been developed for efficient quantification of six selected estrogens in environmental waters. To extract trace estrogens effectively, a poly (1-ally-3-vinylimidazolium chloride-co-ethylene dimethacrylate) monolithic cake was prepared and used as the sorbent of stir cake sorptive extraction (SCSE). The effects of preparation conditions of sorbent and extraction parameters of SCSE for estrogens were investigated and optimized. Under optimal conditions, the developed method showed satisfactory analytical performance for targeted analytes. Low limits of detection (S/N=3) and quantification limits (S/N=10) were achieved within the range of 0.024-0.057 µg/L and 0.08-0.19 µg/L, respectively. Good linearity of method was obtained for analytes with the correlation coefficients (R(2)) above 0.99. At the same time, satisfactory method repeatability and reproducibility was achieved in terms of intra- and inter-day precisions, respectively. Finally, the established SCSE-HPLC/DAD method was successfully applied for the determination of estrogens in different environmental water samples. Recoveries obtained for the determination of estrogens in spiked samples ranged from 71.2% to 108%, with RSDs below 10% in all cases.